By condensation of calix[4]arene 1,3-bis-hydrazide derivative 5 and calix[4]arene mono-benzaldehyde derivative 2, and then intramolecular bridging with triethylene glycol ditosylates, two novel tr/s-calix[4]arenes 6 and 7 containing two kinds of calix[4]arene derivative units were prepared in reasonable yield. When reacting compound 5 with calix[4]arene 1,3-bis-benzaldehyde derivative 3, novel bis-calix[4]arene 8 containing two different calix[4]arene derivative units was obtained in high yield. The extraction experiments showed that the new hosts 6, 7 and 8 possessed excellent complexation abilities towards metal cations and (x-amino acids. Triscalix[4]arene 7 showed good complexation selectivity towards Ag+ and basic α-amino acid. [ABSTRACT FROM AUTHOR]